CN108780837A - Thermo-electric converting material, the thermoelectric conversion device with the thermo-electric converting material, heat chemistry battery and pyroelectric sensor - Google Patents
Thermo-electric converting material, the thermoelectric conversion device with the thermo-electric converting material, heat chemistry battery and pyroelectric sensor Download PDFInfo
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- CN108780837A CN108780837A CN201780015254.2A CN201780015254A CN108780837A CN 108780837 A CN108780837 A CN 108780837A CN 201780015254 A CN201780015254 A CN 201780015254A CN 108780837 A CN108780837 A CN 108780837A
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- converting material
- electric converting
- compound
- cyclodextrin
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 229920000858 Cyclodextrin Polymers 0.000 claims description 52
- 239000003792 electrolyte Substances 0.000 claims description 32
- 150000002500 ions Chemical class 0.000 claims description 27
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 23
- 229920002472 Starch Polymers 0.000 claims description 22
- 239000008107 starch Substances 0.000 claims description 22
- 235000019698 starch Nutrition 0.000 claims description 20
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 15
- 229940006461 iodide ion Drugs 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001338 self-assembly Methods 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 150000001923 cyclic compounds Chemical class 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 claims description 3
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 claims description 3
- -1 ferricyanide ions Chemical class 0.000 claims description 2
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 68
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 36
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 28
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 27
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 19
- 239000001116 FEMA 4028 Substances 0.000 description 17
- 239000003963 antioxidant agent Substances 0.000 description 17
- 230000003078 antioxidant effect Effects 0.000 description 17
- 235000006708 antioxidants Nutrition 0.000 description 17
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 17
- 229960004853 betadex Drugs 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000001103 potassium chloride Substances 0.000 description 15
- 235000011164 potassium chloride Nutrition 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 15
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 230000033116 oxidation-reduction process Effects 0.000 description 11
- 230000014509 gene expression Effects 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 8
- 239000008103 glucose Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229920000856 Amylose Polymers 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000000111 isothermal titration calorimetry Methods 0.000 description 2
- 229960003511 macrogol Drugs 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 229920002560 Polyethylene Glycol 3000 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000005680 Thomson effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
- G01J5/12—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using thermoelectric elements, e.g. thermocouples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/81—Structural details of the junction
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/856—Thermoelectric active materials comprising organic compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
Abstract
The present invention provides thermo-electric converting material, the thermoelectric conversion device with the thermo-electric converting material, heat chemistry battery and the pyroelectric sensor for dramatically increasing Seebeck coefficient.The thermo-electric converting material of the present invention has：Redox couple；And the capture compound for selectively only capturing a side of the redox centering under cryogenic and being discharged under the high temperature conditions.
Description
Technical field
The present invention relates to a kind of thermo-electric converting material, the thermoelectric conversion device with the thermo-electric converting material, heat chemistry electricity
Pond and pyroelectric sensor.
The application in the Japanese Patent Application 2016-046309 of Japanese publication and was claimed priority based on March 9th, 2016,
Its content is applied at herein.
Background technology
In order to which the de minimis energy of waste heat etc. is converted to electric power, thermo-electric converting material attracts attention in recent years.Wherein, as
The energy source of mobile device etc. expects a kind of thin and efficient thermo-electric converting material.However, previous alloy type heat to electricity conversion
Material haves the shortcomings that heat conductivity is high, Seebeck coefficient (Se) is low.Therefore, in recent years, as a kind of thermo-electric converting material
Heat chemistry battery attracts attention (non-patent literature 1), which has used the solution of the redox ion of energy.
The Seebeck coefficient (Se) of previous solid electrothermal alloy is about 0.2mV/K, in contrast, the match of heat chemistry battery
There is seebeck coefficient (Se) value of high an order of magnitude, expectation can be manufactured with low cost.For example, by I-And I3 -The thermalization of composition
It learns in battery, electricity is generated because generating offset under high temperature and cryogenic conditions by the equilibrium potential that redox equilibrium is formed
Position.Its known Seebeck coefficient is about 600 μ V/K, higher than alloy type thermo-electric converting material.However, there are the conductibility of electrolyte
Relatively low problem.It needs to further increase Seebeck coefficient (non-patent literature 2).
Existing technical literature
Non-patent literature
Non-patent literature 1：More J. Abrahams in Theo (Theodore J.Abraham) etc. the, " height for collecting thermal energy
Seebeck coefficient redox ion liquid electrolyte (High Seebeck coefficient redox ionic liquid
Electrolytes for thermal energy harvesting) ", energy and environmental science (Energy &
Environmental Science), (Britain), 2013, volume 6, p.2639-2645；
Non-patent literature 2：More J. Abrahams in Theo (Theodore J.Abraham) etc. the, " Sai Bei in ionic liquid
Foreground (the Seebeck coefficients in ionic liquids-prospects for of gram coefficient-thermoelectrochemistry battery
Thermo-electrochemical cells) ", chemical communication (Chemical Communications), (Britain), 2011
Year, volume 47, p.6260-6262.
Invention content
Problem to be solved by the invention
In order to solve the problem above-mentioned, as the new method for improving Seebeck coefficient, currently invention addresses can be in low temperature
Under the conditions of selectively only capture a side of redox centering and the capture compound that is discharged under the high temperature conditions.As
Redox couple is iodide ion (I-) and teriodide ion (I3 -) in the case of concrete example, be conceived to host-guest
It learns (host-guest chemistry), for example, by the way that cyclodextrin is added in the electrolytic solution, thus I under cryogenic3 -By ring
Dextrin captures, and I under the high temperature conditions3 -It is released, therefore, redox equilibrium potential offset is larger.Its purpose exists as a result,
In, provide it is a kind of raising Seebeck coefficient and improve conversion efficiency of thermoelectric thermo-electric converting material.
The technical method solved the problems, such as
It is a discovery of the invention that selectively only capturing redox centering under cryogenic by adding in the electrolyte
One side and the capture compound discharged under the high temperature conditions can make Seebeck coefficient more than previous thermo-electric converting material
It is high.It is a discovery of the invention that in the case of the concrete example for the heat chemistry battery being made of iodide ion and teriodide ion, lead to
The cyclodextrin that addition captures teriodide ion under cryogenic and discharged under the high temperature conditions is crossed, so as to match
Seebeck coefficient (Se) is improved to 2mV/K or so.
The present invention [1] for example below~[11] are described.
[1] a kind of thermo-electric converting material, which is characterized in that have：
Redox couple；And
Compound is captured, which selectively only captures the one of the redox centering under cryogenic
It is discharged just and under the high temperature conditions.
[2] thermo-electric converting material as described in [1], which is characterized in that the capture compound is from by cyclic compound
And more than at least one selected in the group of helical form compound composition.
[3] thermo-electric converting material as described in any one of [1] or [2], which is characterized in that the capture compound be
The molecule of self assembly under cryogenic conditions.
[4] thermo-electric converting material as described in any one of [1] or [2], which is characterized in that the capture compound is shape
At the host compound of inclusion compound.
[5] thermo-electric converting material as described in [1] or [2], which is characterized in that the capture compound is pasted from by ring
Essence, starch (amylose), polyvinylpyrrolidone and polyethylene glycol oxide composition group in select more than one.
[6] thermo-electric converting material as described in any one of [1]~[5], which is characterized in that the redox couple be from
By iodide ion and teriodide ion, ferrocyanide ion and ferricyanide ions and terpyridyl cobalt (II) and
The a pair selected in the group of terpyridyl cobalt (III) composition.
[7] thermo-electric converting material as described in any one of [1]~[6], which is characterized in that also include to make the capture
The electrolyte of compound self assembly under cryogenic.
[8] a kind of thermoelectric conversion device, wherein with the thermo-electric converting material and one described in any one of [1]~[7]
To electrode.
[9] thermoelectric conversion device as described in [8], which is characterized in that the pair of electrode is set to different temperature.
[10] a kind of heat chemistry battery, which is characterized in that including the thermoelectric conversion device described in [8] or [9].
[11] a kind of pyroelectric sensor, which is characterized in that including the thermoelectric conversion device described in [8] or [9].
Invention effect
According to the present invention, redox centering is selectively only captured under cryogenic by adding in the electrolyte
One side and the capture compound discharged under the high temperature conditions can make Seebeck coefficient more than previous thermo-electric converting material
It is high.In particular, by adding cyclodextrin in the heat chemistry battery being made of iodide ion and teriodide ion, can make
Seebeck coefficient is improved to 2000 μ V/K or so.
Description of the drawings
Fig. 1 is the concept map for the thermoelectric conversion device for indicating the thermo-electric converting material with the present invention.
Fig. 2 is to indicate selectively to include I by alpha-cyclodextrin3 -Concept map.
Fig. 3 is indicated by adding alpha-cyclodextrin (α-CD) to include I in low temperature side first electrode property selected around3 -
Concept map.
Fig. 4 is the addition concentration ([α-CD] for indicating alpha-cyclodextrin0) and I3 -Addition concentration ([I3 -]0) ratio ([α-CD
]0/[I3 -]0) and Seebeck coefficient (Se) relationship figure.
Fig. 5 is to indicate alpha-cyclodextrin and I in the system comprising potassium ion3 -Inclusion compound further with potassium ion self assembly
Concept map.
Fig. 6 is the figure of the complex concentration in the solution for indicating to be evaluated according to the absorbance of the 353nm of complex compound.
Fig. 7 is alpha-cyclodextrin (α-CD), beta-cyclodextrin (β-CD), gamma-cyclodextrin (γ-CD) and I3 -Ion forms inclusion compound
Binding constant Arrhenius figure.
Fig. 8 is the concept map of the amylose sucking iodine for the main component for being denoted as starch.
Fig. 9 is variation (the observation wavelength of absorbance caused by indicating iodine-starch complex compound：Figure 552nm).
Figure 10 is the concept map indicated using the heat chemistry battery of embodiment 1 made of H-type container.
Figure 11 is the evaluation figure of the Seebeck coefficient of embodiment 1.
Figure 12 is the figure for indicating the Seebeck coefficient (solid line, mV/K) after addition HCl.
Figure 13 is to indicate I3 -Increase (the electrolyte of power density caused by inclusion：HCl figure).
Figure 14 is to have recorded the figure for being added and having the power density of the battery of α-CD and electrolyte to change over time.
Figure 15 is the figure for indicating the Seebeck coefficient (solid line, mV/K) after addition KCl.
Figure 16 is the microscope photo of acicular crystal.
Figure 17 is to indicate K [(α-CD)2-I5] crystalline texture figure.
Figure 18 is to indicate I3 -Increase (the electrolyte of power density caused by inclusion：KCl figure).
Figure 19 A are the concentration and I for indicating α-CD3 -The relational graph of the ratio and Seebeck coefficient (Se) of concentration.Concentration conditions：
[CD]=0~5mM；[I3 -]=2.5mM；[I-]=10mM；[KCl]=0.200mM.
Figure 19 B are the concentration and I for indicating β-CD3 -The relational graph of the ratio and Seebeck coefficient (Se) of concentration.Concentration conditions：
[CD]=0~5mM；[I3 -]=2.5mM；[I-]=10mM；[KCl]=0.200mM.
Figure 19 C are the concentration and I for indicating γ-CD3 -The relational graph of the ratio and Seebeck coefficient (Se) of concentration.Concentration conditions：
[CD]=0~5mM；[I3 -]=2.5mM；[I-]=10mM；[KCl]=0.200mM.
Figure 19 D are the relational graphs for the concentration for indicating Seebeck coefficient (Se) and five kinds of host molecules.Concentration conditions：[CD]=
0~8mM；[I3 -]=2.5mM；[I-]=10mM.
Figure 20 is current density/power density-voltage curve in the case of being not added with KCl.
Figure 21 is current density/power density-voltage curve in the case of the KCl for adding 200mM.
Figure 22 is the figure for evaluating Seebeck coefficient.
Figure 23 is to indicate starch concentration (converting with 6 glucose) and I3 -The ratio of concentration and the relational graph of Seebeck coefficient.
Figure 24 is that the power in the case that the addition in the embodiment 5 for indicate addition starch has the KCl of 0.2M becomes at any time
The figure of change.
Figure 25 be indicate Seebeck coefficient (Se) and Macrogol 3000 (PEG3000) concentration (converted with monomer,
mMMonomer) relational graph.
Figure 26 be Seebeck coefficient (Se) with the concentration of polyvinylpyrrolidone (PVP) (converted with monomer, mMMonomer) pass
System's figure.
Figure 27 is the figure for evaluating Seebeck coefficient.
Specific implementation mode
< thermo-electric converting materials >
The thermo-electric converting material of the present invention has：Redox couple；And institute is selectively only captured under cryogenic
The capture compound stated a side of redox centering and discharged under the high temperature conditions.It should be noted that in this explanation
In book, " thermo-electric converting material " refers to that heat is directly changed into electricity or electricity is directly changed into the material of heat, for example, referring to
It can be used in using the equipment of Seebeck effect, the equipment using peltier effect, equipment using Thomson effect etc.
Material.Fig. 1 is the concept map for the thermoelectric conversion device for indicating the thermo-electric converting material with the present invention.
As aforementioned capture compound, as long as selectively only capturing aforementioned oxidation reduction centering under cryogenic
As soon as side and the capture compound discharged under the high temperature conditions, there is no particular limitation, for example, can enumerate can will capture
Object is contained in the macromolecule etc. of cyclic compound, helical form compound in compound etc..In addition, for example, if by aforementioned
Capture compound under cryogenic self assembly and the aggregate that constitutes selectively can only capture under cryogenic it is aforementioned
One side of redox centering and discharged under the high temperature conditions, then can be by aforementioned capture compound under cryogenic
The compound of self assembly.The cyclic compound is, for example, cyclodextrin, and the helical form compound is, for example, starch.It is preferred that aforementioned
It is from the group being made of cyclodextrin, starch, polyvinylpyrrolidone, polyethylene glycol oxide and polyethylene glycol etc. to capture compound
Select more than one, more preferably cyclodextrin.
Aforementioned oxidation is restored to being made of anti-oxidant active kind and reducing agent reactive species.It can be by reduction reaction by aoxidizing
Agent reactive species are reduced to reducing agent reactive species or are oxidized to anti-oxidant active kind by reducing agent reactive species by oxidation reaction.
It is preferred that aforementioned oxidation is restored to being a pair selected from the group being made of iodide ion and teriodide ion etc., more preferably
For iodide ion and teriodide ion.
The thermo-electric converting material of the present invention includes ionic electrolyte, and preferably the ionic electrolyte is ionic liquid, more
Preferably include the water solvent or water of water and organic solvent.For example, when ionic electrolyte is water solvent or water, it is special
Sign is that in water solvent or water redox reaction occurs for redox couple, moreover, aforementioned capture compound is molten in water system
A side of aforementioned oxidation reduction centering is selectively only captured in agent or water under cryogenic and is released under the high temperature conditions
It puts.
Ionic electrolyte can also include the ion in addition to redox couple.For example, when ionic electrolyte is water
When series solvent or water, alkali ion is preferably comprised.
Further, it is preferable to include the electrolyte for making aforementioned capture compound self assembly under cryogenic.
When aforementioned redox couple is iodide ion and teriodide ion, captures compound and be preferably capable capturing
The cyclodextrin of teriodide ion, more preferably alpha-cyclodextrin.Preferred ion electrolyte is water solvent or water.It is preferred that water system
Solvent or water also include alkali ion.
< thermoelectric conversion devices >
The thermoelectric conversion device of the present invention has aforementioned thermo-electric converting material and a pair of electrodes.It should be noted that " heat
Electrical switching device " refer to include all of the Sai Beike elements of thermo-electric converting material, Peltier's element etc. can will be hot
Can and electric energy mutually convert thermoelectric conversion element, using thermo-electric converting material known device device.
The present invention thermoelectric conversion device for example with：Redox couple；Before selectively only capturing under cryogenic
The capture compound stated a side of redox centering and discharged under the high temperature conditions；Ionic electrolyte；First electrode；
And second electrode, moreover, at least part of surface and second electrode of aforesaid electrolyte and aforementioned first electrode are at least
The surface physics contact of a part.
< < capture compound > >
As long as capture compound be under cryogenic selectively only capture aforementioned oxidation reduction centering a side and
The capture compound discharged under hot conditions, just there is no particular limitation, is accommodated for example, can enumerate and can will capture object
The macromolecule etc. of cyclic compound, helical form compound in compound etc..In addition, preferably being wrapped for example, capturing compound
It closes and captures object to form the host compound of inclusion compound.In addition, for example, if by aforementioned capture compound in cryogenic conditions
Lower self assembly and the aggregate that constitutes selectively can only capture under cryogenic a side of aforementioned oxidation reduction centering and
It is discharged under the high temperature conditions, then can be by the compound of aforementioned capture compound self assembly under cryogenic.The ring
Shape compound is, for example, cyclodextrin, which is, for example, starch, polyvinylpyrrolidone, polyethylene glycol oxide.In addition,
The host compound is, for example, cyclodextrin, starch, polyvinylpyrrolidone, polyethylene glycol oxide.It is preferred that aforementioned capture compound is
Selected from the group being made of cyclodextrin, starch, polyvinylpyrrolidone, polyethylene glycol oxide and polyethylene glycol etc. it is a kind of with
On, more preferably cyclodextrin.
As cyclodextrin, for example, can enumerate from by alpha-cyclodextrin (α-CD), beta-cyclodextrin (β-CD), gamma-cyclodextrin (γ-
CD), six-(2,6- bis--O- methyl)-alpha-cyclodextrins (Di-O-Me- α-CD) and six-(2,3,6- tri--O- methyl)-α-rings paste
The one or more kinds of compounds selected in the group of smart (Tri-O-Me- α-CD) composition.More preferably from by alpha-cyclodextrin (α-
CD), six-(2,6- bis--O- methyl)-alpha-cyclodextrins (Di-O-Me- α-CD) and six-(2,3,6- tri--O- methyl)-α-rings paste
The one or more kinds of compounds selected in the group of smart (Tri-O-Me- α-CD) composition.
< < redox couple > >
Aforementioned oxidation is restored to being made of anti-oxidant active kind and reducing agent reactive species.It can be by reduction reaction by aoxidizing
Agent reactive species are reduced to reducing agent reactive species or are oxidized to anti-oxidant active kind by reducing agent reactive species by oxidation reaction.
Aforementioned oxidation reduction to preferably from by iodide ion and teriodide ion, the ferrocyanide ion and iron cyanide from
Son, terpyridyl cobalt (II) and terpyridyl cobalt (III) and ferrocene (ferrocen) monocarboxylic acid (FeII) and ferrocene
(ferrocenium) a pair for selecting in the group of monocarboxylic acid (FeIII) composition, more preferably iodide ion and teriodide from
Son.
The ionic electrolyte > > of < <
Ionic electrolyte is preferably ionic liquid, ionic solid, more preferably includes the water system of water and organic solvent
Solvent or water.For example, when ionic electrolyte is water solvent or water, which is characterized in that redox couple is in water solvent
Or redox reaction occurs in water, moreover, aforementioned capture compound is selective under cryogenic in water solvent or water
Ground only captures a side of aforementioned oxidation reduction centering and is discharged under the high temperature conditions.It is preferred that water system electrolyte also includes potassium etc.
Alkali ion.
< < first electrodes or second electrode > >
The material of a part of surface portion as the first electrode or second electrode contacted with aforesaid electrolyte, can enumerate
The conductive materials such as platinum or carbon, but the preferably platinum of dissolution potential height and excellent corrosion resistance.In addition, and surface area low from manufacturing cost
From the perspective of big, the preferred carbon of graphite etc..
The thermoelectric conversion device > > of < < first embodiments
For example, in first electrode aforementioned oxidation occurs for the thermoelectric conversion device of the first embodiment as the present invention also
The reducing agent of one side of former centering becomes the oxidation reaction of the oxidant of another party, and in aforementioned second electrode, aforementioned oxidation occurs
Agent becomes the reduction reaction of aforementioned reducing agent.It can enumerate between first electrode and second electrode that there are temperature difference and the temperature differences
Lead to the hair for generating the Sai Beike elements of potential difference to generate thermo-electromotive force between aforementioned first electrode and second electrode etc.
Electric installation.
The thermoelectric conversion device > > of < < second embodiments
As the thermoelectric conversion device of second embodiment of the present invention, for example, in first electrode, aforementioned oxidation occurs also
The reducing agent of one side of former centering becomes the oxidation reaction of the oxidant of another party, in aforementioned second electrode, makes aforementioned oxygen
Agent becomes the reduction reaction of aforementioned reducing agent.Can enumerate between aforementioned first electrode and second electrode there are potential difference and should
Potential difference causes to generate temperature difference to generate the mobile Peltier's element etc. of heat between aforementioned first electrode and second electrode
Cooling/heating device.
The thermoelectric conversion device > > of < < third embodiments
As the thermoelectric conversion device of third embodiment of the present invention, for example, the aforementioned first electrode in low temperature side is sent out
The oxidation reaction of raw redox couple, occurs the reduction reaction of aforementioned oxidation reduction pair in the aforementioned second electrode of high temperature side.
It can enumerate and capture the anti-oxidant active kind of compound capture aforementioned oxidation reduction pair, make between aforementioned first electrode and second electrode
Generate the n-type Sai Beike elements of thermo-electromotive force.
The thermoelectric conversion device > > of the 4th embodiments of < <
The thermoelectric conversion device of the 4th embodiment of the present invention is for example with iodide ion and teriodide ion, ring
Dextrin and water or water solvent, but also the second electrode of first electrode and high temperature side with low temperature side.Water system electrolyte
Contacted at least part surface physics at least part surface of first electrode and second electrode, at least with electrolyte contacts
The material of electrode surface part be the conductive materials such as platinum or carbon.Wherein, particularly preferred dissolution potential height and excellent corrosion resistance
Platinum.In addition, from the viewpoint of manufacturing cost is low and surface area is big, the preferred carbon of graphite etc..
Preferably also include the alkali ion of potassium etc. as water system electrolyte.
< heat chemistrys battery (thermo-electrochemical cell) >
The heat chemistry battery (thermo-electrochemical cell) of the present invention has：Bake element is matched, this is utilized
The thermo-electric converting material of invention occurs due to the temperature difference between first electrode and second electrode in first electrode and second electrode
Redox reaction generates potential difference between first electrode and second electrode.
Match Bake element is evaluated by Seebeck coefficient (Se) shown in following mathematical expressions 1.
Mathematical expression 1
(in formula, Δ E is interelectrode potential difference, and Δ T is temperature difference.)
Thermo-electric converting material has possessed by the heat chemistry battery of the present invention：Redox couple；And in cryogenic conditions
Under selectively only capture a side of aforementioned oxidation reduction centering and the capture compound that is discharged under the high temperature conditions.According to
The anti-oxidant active kind concentration ([Ox]) of redox couple, reducing agent reactive species concentration ([Red]) and electrode temperature (T), standard
The relationship of current potential (Ef), the oxidation-reduction potential (E) of first electrode or second electrode, redox couple can be by being used as energy
Following mathematical expressions (2) of this special formula indicate.
Mathematical expression 2
As shown in formula (2), the oxidation-reduction potential (E) of redox couple depends on normal potential (Ef), temperature, oxidation also
Former pair of anti-oxidant active kind concentration ([Ox]) and reducing agent reactive species concentration ([Red]).
The present invention by comprising under cryogenic selectively only capture redox centering a side and in high temperature item
The capture compound discharged under part, to which for example near the first electrode of low temperature side, capture generates in the oxidation reaction
Anti-oxidant active kind, make anti-oxidant active kind concentration ([Ox]) reduce.Near the second electrode of high temperature, release is as reduction
The anti-oxidant active kind of the reactant of reaction makes anti-oxidant active kind concentration ([Ox]) increase.As a result, generating first electrode
It is poor with the anti-oxidant active kind concentration ([Ox]) near second electrode nearby, with the previous temperature difference electricity without capture compound
Pond is compared, and the potential difference of first electrode and second electrode is generated using concentration difference.
The heat chemistry battery > > of < < first embodiments
[addition of cyclodextrin]
The heat chemistry battery of the first embodiment of the present invention has iodide ion and teriodide ion, α-ring paste
Essence and water or water solvent, but also the second electrode of first electrode and high temperature side with low temperature side.
[I is included by alpha-cyclodextrin3 -]
I is included for the alpha-cyclodextrin by being indicated by chemical formula (1)3 -For, as covered in the prior art as,
Selectively include hydrophobic I3 -, rather than hydrophilic I-。
Chemical formula 1
Fig. 2 is to indicate selectively to include I by alpha-cyclodextrin near low temperature lateral electrode3 -Concept map.
Near the first electrode of low temperature side, capture in oxidation reaction (I-/I3 -) in generate anti-oxidant active kind I3 -, make
Anti-oxidant active kind concentration ([I3 -]) reduce.Near the second electrode of high temperature, release is used as reduction reaction (I3 -/I-) reaction
The anti-oxidant active kind of object makes anti-oxidant active kind concentration ([I3 -]) increase.As a result, generating first electrode nearby with second
Anti-oxidant active kind concentration ([I near electrode3 -]) poor, compared with without the previous temperature difference battery for capturing compound, make
Increase the potential difference (mathematical expression 3) of first electrode and second electrode with concentration difference.
Mathematical expression 3
According to following mathematical expressions (4) as nernst equation, current potential depends on concentration, therefore, when there are concentration difference,
Potential difference increases (as shown in Figure 3).
Mathematical expression 4
Fig. 3 is to indicate to include I in low temperature side first electrode property selected around by adding alpha-cyclodextrin (α-CD)3 -'s
Concept map.
As a result, by adding alpha-cyclodextrin, it be that 3 times before adding are up to about 2mV/ that can obtain Seebeck coefficient
The value of K.
[relative concentration and Seebeck coefficient that capture compound]
Fig. 4 is to indicate that alpha-cyclodextrin adds concentration ([α-CD]0) and I3 -Addition concentration ([I3 -]0) ratio ([α-CD]0/
[I3 -]0) and Seebeck coefficient (Se) relationship and the I that does not include3 -Concentration and [α-CD]0/[I3 -]0Relationship figure.Such as
Shown in Fig. 4, at [α-CD]0/[I3 -]0After > 1, by 10 DEG C of first electrodes (dotted line) and 40 DEG C of second electrode (solid line) table
The I not included shown3 -Concentration difference become larger.
α-the CD and I that will be acquired according to identical titration calorimetry3 -Binding constant be shown in following table 1.When temperature rise 30
DEG C when, α-CD and I3 -Binding constant reduce 12%.
Table 1
α-CD and I3 -Binding constant (identical titration calorimetry)
| 10℃ | 40℃ |
| 3.7×105 | 4.4×104 |
The solid line of Fig. 4 is to carry out the Seebeck coefficient (Se) that simulation acquires by being used as the mathematical expression of nernst equation (5).
Show I3 -Concentration difference cause Seebeck coefficient to increase.
Mathematical expression 5
The heat chemistry battery > > of < < second embodiments
[influence of the supporting electrolyte to Seebeck coefficient]
For the heat chemistry battery of second embodiment of the present invention, in addition to further add potassium ion etc. alkalinity from
It is identical as the heat chemistry battery of first embodiment other than son.By adding alkali ion, higher match Bake system can be obtained
Number.
For example, by adding potassium ion (K+), near first electrode, generate bottle-green precipitation K [(α-CD)2-I5],
Make I3 -Concentration be further reduced.The amount of precipitation near low temperature side first electrode is than the precipitation capacity near high temperature side second electrode
It is more.Precipitation generates and causes I3 -Concentration difference expand.As a result, Seebeck coefficient increases to maximum 1.96mV/K.Obtain the match
The reason of seebeck coefficient, there is at following 3 points.(Fig. 5)
(1) self assembly (generate precipitation) under cryogenic.
(2) complex concentration in solution is lower.
(3) I under cryogenic conditions3 -Concentration further decreases.
Fig. 5 is to indicate alpha-cyclodextrin and I in the system comprising potassium ion3 -Inclusion compound further with potassium ion from group
The concept map of dress.
Fig. 6 is indicated according to alpha-cyclodextrin and I3 -Absorbance of the complex compound at 353nm and the network in the solution evaluated
Close the figure of object concentration.In low temperature side alpha-cyclodextrin and I3 -Complex compound carry out self assembly, the concentration in solution reduces.
According to Fig. 6, the feelings not precipitated in the case of having precipitation when by first electrode be 10 DEG C, second electrode is 40 DEG C and
I under condition3 -The data of concentration be shown in table 2.
Table 2
I3 -Concentration [mM]
| 10℃ | 40℃ | Concentration ratio | |
| There is precipitation | 9.9×10-4 | 2.6×10-2 | 26 times |
| Without precipitation | 4.2×10-3 | 3.2×10-2 | 7.6 again |
It is therefore contemplated that Seebeck coefficient is increased the reason is that, the generation of precipitation causes I when addition potassium ion3 -Concentration
Difference expands.
The heat chemistry battery > > of < < third embodiment of the present invention and the 4th embodiment
[comparing the effect between α-CD, β-CD, γ-CD]
For the heat chemistry battery of third embodiment of the present invention and the 4th embodiment, in addition to using β-respectively
Cyclodextrin (β-CD), gamma-cyclodextrin (γ-CD) replace other than alpha-cyclodextrin (α-CD), the heat chemistry with first embodiment
Battery is identical.
By alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and I3 -Ion forms the Arrhenius of the binding constant of inclusion compound
It is illustrated in Fig. 7.Beta-cyclodextrin and gamma-cyclodextrin without the binding constant as alpha-cyclodextrin, but have certain temperature according to
Lai Xing.
Heat chemistry battery with beta-cyclodextrin, gamma-cyclodextrin is unable to get high Sai Beike systems as alpha-cyclodextrin
Number (Se).But compared with the heat chemistry battery of not cyclodextrin, higher Seebeck coefficient (Se) is shown.
Fig. 7 is alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and I3 -Ion forms the Ah Lei Buddhist nun of the binding constant of inclusion compound
Wu Situ.
As shown in fig. 7, in the same manner as alpha-cyclodextrin (α-CD), when adding beta-cyclodextrin (β-CD), β-CD-I are formed3 -Packet
Object is closed, for example, in the case of the beta-cyclodextrin of 4mM, Se 1.1mV/K.As further addition K+When, precipitation generates, and Se is
1.5mV/K.When adding gamma-cyclodextrin, γ-CD-I are formed3 -Inclusion compound, Se 0.92mV/K.But even if further addition
K+, precipitation will not be generated.Se is 1.0mV/K.
The heat chemistry battery > > of the 5th embodiment of the < < present invention
[using starch as capture compound]
For the present invention the 5th embodiment heat chemistry battery for, in addition to use amylose (starch it is main
Ingredient) it replaces other than cyclodextrin, it is as the heat chemistry battery of first embodiment identical.It has been similarly observed that Seebeck coefficient
Improvement effect.
The amylose of main component as starch is included in (capture) iodine as Fig. 8.
Amylose (starch) is similarly it is observed that the improvement effect of Seebeck coefficient.
Fig. 9 is the figure for the variation (observation wavelength 552nm) for indicating the absorbance caused by iodine-starch complex compound.Work as temperature
When rising, concentration is reduced, and upon a drop in temperature, concentration increases.
For the heat chemistry battery of the 5th embodiment of the present invention, in the same manner as first embodiment, the addition of starch
Seebeck coefficient is caused to increase.
< pyroelectric sensors >
The pyroelectric sensor of the present invention is each thermo-electric converting material using the present invention above-mentioned come the temperature between sensing electrode
Spend the device of difference.Since the Seebeck coefficient of the thermo-electric converting material of the present invention is high, the sensitivity as temperature sensor
It is high.For example, can enumerate by use include aforementioned alpha-cyclodextrin and with iodide ion and teriodide ion and potassium from
The thermo-electric converting material of the aqueous solution of son and the pyroelectric sensor that there is the thermoelectric conversion device of the first and second platinum electrodes to constitute.
In the case of this pyroelectric sensor, the electricity of 2mV can be generated the first and second interelectrode temperature differences are only 1 DEG C
Pressure.The device that potential difference is measured by good potentiometer of connection precision etc. can be constructed to 0.000001 DEG C or so of identification
The sensor of difference.If the temperature difference of the degree can be identified, such as transmitted from the body temperature of the people positioned at the other side of wall
Heat one electrode is heated, can sense when people.In addition, the faint infrared ray radiated from heat source can be sensed.This
Outside, it in material of the electrode side setting specific light such as can absorb ultraviolet light to fever, can be applied to
Sense the pyroelectric sensor of faint light.
Embodiment
(embodiment 1)
The preparation > of < electrolyte
In the H-type container of tool as shown in Figure 10 there are two test tube, I is added2(317mg, 1.25mmol), KI
(415mg, 2.50mmol) and water, are prepared into [KI3] 50mM, [KI] 50mM solution.It is added in the 2.5ml solution
After the α-CD (25mM) of 0.2mmol, is diluted with KI aqueous solutions, obtain 2.5mM [KI3], the solution of 10mM [KI], 4mM [α-CD].
The first test tube in two test tubes of H-type is placed in ice bath, and the temperature near first electrode is maintained at 10 DEG C, by second
Test tube is placed in the thermostat that can adjust temperature at 10~50 DEG C, and the temperature near second electrode is adjusted to 10~50 DEG C.
The composition > of < batteries
Comprising by 2.5mM [KI3], 10mM [KI] and 4mM [α-CD] composition aqueous solution the first test tube and second
Platinum filament is inserted into test tube respectively.
< I3 -Inclusion caused by Seebeck coefficient increase >
Seebeck coefficient is acquired according to the slope of straight line shown in Figure 11.When alpha-cyclodextrin is added, Seebeck coefficient from
0.86mV/K increases to 1.43m/K.
(embodiment 2)
It is same as Example 1 other than addition HCl (0.1M) for embodiment 2.Figure 12 is to indicate addition HCl
The figure of Seebeck coefficient (solid line) [mV/K] afterwards.Similarly to Example 1, according to Figure 12, Seebeck coefficient (Se) never adds
0.56mV/K when α-CD is added to increase to 1.16 after addition.The comparison with embodiment 1 is also shown in Figure 12.The addition of HCl is drawn
Play I3 -/I-Activity changes.When adding α-CD, Se is reduced from 1.43mV/K to 1.16mV/K；When being not added with α-CD, Se
It is reduced from 0.86mV/K to 0.56mV/K.
Power density increases (electrolyte caused by < inclusions：HCl) >
By adding α-CD, the increase of open-circuit voltage (Voc) and the increase of output power density are observed.
Figure 13 is to indicate I3 -Inclusion causes the increase (electrolyte of power density：HCl figure).
< power densities change with time and (have α-CD) >
Figure 14 is to have recorded addition to have α-CD and electrolyte (◇：HCl the figure that the power density of battery) changes over time.
(embodiment 3)
It is same as Example 1 other than addition KCl (0.2M) for embodiment 3.Figure 15 is to indicate addition KCl
The figure of Seebeck coefficient (solid line, mV/K) afterwards.Similarly to Example 1, in fig.15, Seebeck coefficient (Se) never adds
0.86mV/K when α-CD is added to increase to the 1.96mV/K after addition.The comparison with embodiment 1 is also shown in Figure 15.Add KCl
Do not cause I3 -/I-Activity change.When adding α-CD, Se increases to 1.96mV/K from 1.43mV/K；When being not added with
When α-CD, Se does not change, and is 0.86mV/K.
In embodiment 3, different from embodiment 1,2, observe bottle-green precipitation K [(α-CD)2-I5].Think precipitation
Generate the increase for resulting in Seebeck coefficient.
< K [(α-CD)2-I5] crystalline texture >
In order to identify bottle-green sediment, aqueous solution below is prepared, and evaluate the structure of the sediment.Water
Each ion concentration in solution is as follows.
[I3 -]0=[I-]0=8mM,
[α-CD]0=4mM,
[KCl]=80mM
By above-mentioned solution left standstill two days, acicular crystal (Figure 16) is obtained.The crystalline texture passes through X-ray diffraction device
(XRD) it measures, its analysis result is shown in Figure 17.
[power density caused by inclusion increases (electrolyte：KCl)]
As shown in figure 18, by adding α-CD, the increasing of the increase and output power density of open-circuit voltage (Voc) is observed
Add.
[power density changes with time and (has α-CD)]
Figure 14 is to have recorded addition to have α-CD and electrolyte (zero：KCl the figure that the power density of battery) changes over time.
(embodiment 4)
The additive effect > of < α-CD, β-CD, γ-CD, Di-O-Me- α-CD, Tri-O-Me- α-CD
For the heat chemistry battery of embodiment 4, in addition to using beta-cyclodextrin (β-CD), gamma-cyclodextrin (γ-respectively
CD), six-(2,6- bis--O- methyl)-alpha-cyclodextrins (Di-O-Me- α-CD), six-(2,3,6- tri--O- methyl)-alpha-cyclodextrins
(Tri-O-Me- α-CD) is replaced other than alpha-cyclodextrin (α-CD), identical as the heat chemistry battery of embodiment 1.
Figure 19 A, 19B, 19C are the relational graphs for the relative concentration for indicating Seebeck coefficient and host molecule, and cyclodextrin adds
Add concentration ([CD]0) it is 0~5mM, addition the concentration ([I of teriodide ion3 -]0) it is 2.5mM, the concentration of iodide ion
([I-]) it is 10mM, the concentration ([KCl]) of potassium chloride is 0.200mM.
As shown in Figure 19 A, 19B, 19C, in the same manner as alpha-cyclodextrin, when adding beta-cyclodextrin, β-CD-I are formed3 -Inclusion
Object, for example, in the case of the beta-cyclodextrin of 4mM, Se 1.1mV/K.As further addition K+When, precipitation generates, and Se is
1.5mV/K.When adding gamma-cyclodextrin, γ-CD-I are formed3 -Inclusion compound, for example, in the case of the beta-cyclodextrin of 4mM, Se
For 1.1mV/K.As further addition K+When, precipitation is not generated.
Figure 19 D are the relational graph for the concentration for indicating Seebeck coefficient and five kinds of host molecules, the addition concentration of cyclodextrin
([CD]0) it is 0~8mM, addition the concentration ([I of teriodide ion3 -]0) it is 2.5mM, the concentration ([I of iodide ion-]) be
10mM。
As shown in figure 19 D, in the same manner as alpha-cyclodextrin, when adding beta-cyclodextrin, β-CD-I are formed3 -Inclusion compound, for example,
In the case of the beta-cyclodextrin of 4mM, Se 1.1mV/K.When adding gamma-cyclodextrin, γ-CD-I are formed3 -Inclusion compound, example
Such as, in the case of the gamma-cyclodextrin of 4mM, Se 0.8mV/K.When adding six-(2,6- bis--O- methyl)-alpha-cyclodextrins,
Form Di-O-Me- α-CD-I3 -Inclusion compound, for example, in the case of six-(2 6-, bis--O- methyl)-alpha-cyclodextrins of 4mM, Se
For 1.5mV/K.When adding six-(2,3,6- tri--O- methyl)-alpha-cyclodextrins, Tri-O-Me- α-CD-I are formed3 -Inclusion compound, example
Such as, in the case of the Tri-O-Me- α-CD of 4mM, Se 1.85mV/K.
The comparison > of current density/power density-voltage curve between < α-CD, β-CD, γ-CD
Figure 20 is the figure of current density/power density-voltage curve when KCl not being added.The concentration of each ion of solution
It is as follows.
×：[CD]=0mM
[I3 -]=2.5mM
[I-]=10mM
◇：Add γ-CD
△：Add β-CD
○：Add α-CD
Solid line：Power density-voltage curve
Dotted line：Current density voltage curve
Figure 21 is the figure of current density/power density-voltage curve when adding the KCl of 200mM.Each ion of solution
Concentration is as follows.
×：[CD]=0mM
[I3 -]=2.5mM
[I-]=10mM
[KCl]=200mM
▽：[CD]=0mM
[I3 -]=50mM
[I-]=50mM
△：In × middle addition β-CD
○：In × middle addition α-CD
Solid line：Power density-voltage curve
Dotted line：Current density voltage curve
According to the above results, the case where β-CD and the γ-CD for using the emptying aperture bigger compared with α bodies are used as host molecule
Under, it also shows to reflect respectively and I3 -Binding constant Seebeck coefficient variation.
(embodiment 5)
For embodiment 5, be calculated as 0 in addition to addition concentration is added with glucose conversion, 30,60mM (changes with glucose
Calculate) starch replace other than cyclodextrin, it is same as Example 1.Carry out Seebeck coefficient evaluation, to be added addition concentration with
Glucose conversion is calculated as 0,30, the open-circuit voltage (Voc) after the starch of 60mM (being converted with glucose) and interelectrode temperature difference
Relationship evaluated, acquire Seebeck coefficient as shown in figure 22.
Figure 23 is to indicate starch concentration (being converted into the concentration of 6 glucose, 6 glucose) and I3 -The ratio of concentration ([6
Glucose]/[I3 -]) and Seebeck coefficient relational graph.
< power densities change with time (starch) >
Figure 24 is that power density when indicating that the KCl of 0.2M is added in the present embodiment for adding starch changes over time
Figure.In order to be compared, the power when KCl that 0.2M is added in the embodiment 3 added with alpha-cyclodextrin is also described together
Density changes with time.
(embodiment 6)
For embodiment 6, in addition to adding Macrogol 4000 (bank field Chemical Co., Ltd. (キ シ ダ chemistry strain formulas
Commercial firm) system, average molecular weight is by 2700~3400) (PEG4000) replace other than cyclodextrin, similarly to Example 1 carry out
The evaluation of Seebeck coefficient.Figure 26 be indicate Seebeck coefficient and Macrogol 3000 concentration (converted with monomer, mMMonomer)
The figure of relationship.As shown in figure 26, when addition concentration is calculated as 10mM with monomer conversion, Seebeck coefficient 1.35mV/K.
(embodiment 7)
For embodiment 7, in addition to adding polyvinylpyrrolidone (bank field Chemical Co., Ltd. (キ シ ダ chemistry strains
Formula commercial firm) it makes, molecular weight is replaced by 40000) (PVP) other than cyclodextrin, carries out Seebeck coefficient similarly to Example 1
Evaluation.Figure 27 is concentration (concentration in terms of monomer conversion, the mM for indicating Seebeck coefficient and polyvinylpyrrolidoneMonomer) pass
System's figure.When addition concentration is calculated as 20mM with monomer conversion, Seebeck coefficient 1.15mV/K.
(embodiment 8)
For embodiment 8, ferrocene monocarboxylic acid (FeII) (Sigma-Aldrich's (シ グ マ ア Le is used
De リ ッ チ societies) system) and replace as oxidation as ferrocene (ferrocenium) monocarboxylic acid (FeIII) of its oxysome
The iodide ion and teriodide ion of reduction pair, and beta-cyclodextrin is added to replace alpha-cyclodextrin, in addition to this, with reality
Apply the evaluation that example 1 is carried out similarly Seebeck coefficient.When as shown in figure 27, to no beta-cyclodextrin and it is added to the β-of 2.0mM
Open-circuit voltage (Voc) and the relationship of interelectrode temperature difference (Δ T) after cyclodextrin are evaluated, each Seebeck coefficient be-
0.98mV/K and -1.20mV/K.It confirmed that beta-cyclodextrin selectively captures the ferrocene monocarboxylic acid (FeII) as Reduction Body.
Claims (11)
1. a kind of thermo-electric converting material, which is characterized in that have：
Redox couple；And
Capture compound, the capture compound selectively only capture under cryogenic a side of the redox centering and
It is discharged under the high temperature conditions.
2. thermo-electric converting material as described in claim 1, which is characterized in that the capture compound is from by cyclic compound
And more than at least one selected in the group of helical form compound composition.
3. thermo-electric converting material as claimed in claim 1 or 2, which is characterized in that the capture compound is in cryogenic conditions
The molecule of lower self assembly.
4. thermo-electric converting material as claimed in claim 1 or 2, which is characterized in that the capture compound is to form inclusion compound
Host compound.
5. thermo-electric converting material as claimed in claim 1 or 2, which is characterized in that the capture compound be from by cyclodextrin,
Starch, polyvinylpyrrolidone and polyethylene glycol oxide composition group in select more than one.
6. such as thermo-electric converting material according to any one of claims 1 to 5, which is characterized in that the redox couple be from
By iodide ion and teriodide ion, ferrocyanide ion and ferricyanide ions and terpyridyl cobalt (II) and
The a pair selected in the group of terpyridyl cobalt (III) composition.
7. such as thermo-electric converting material according to any one of claims 1 to 6, which is characterized in that also include to make the captureization
Close the electrolyte of object self assembly under cryogenic.
8. a kind of thermoelectric conversion device, wherein have thermo-electric converting material according to any one of claims 1 to 7 and one
To electrode.
9. thermoelectric conversion device as claimed in claim 8, which is characterized in that the pair of electrode is set to different temperature
Degree.
10. a kind of heat chemistry battery, which is characterized in that including the thermoelectric conversion device described in claim 8 or 9.
11. a kind of pyroelectric sensor, which is characterized in that including the thermoelectric conversion device described in claim 8 or 9.
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| PCT/JP2017/009511 WO2017155046A1 (en) | 2016-03-09 | 2017-03-09 | Thermoelectric conversion material, and thermoelectric conversion device, thermochemical battery and thermoelectric sensor having said material |
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| CN112713233B (en) * | 2019-10-25 | 2023-09-26 | 南方科技大学 | Quasi-solid ionic thermoelectric conversion material, thermoelectric conversion device and application thereof |
| JPWO2021235526A1 (en) * | 2020-05-21 | 2021-11-25 | ||
| ES2934182B2 (en) * | 2021-07-20 | 2023-12-11 | Univ Jaume I | THERMOELECTRIC DEVICE INFLUENCED BY REDOX SPECIES |
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| EP3428984A4 (en) | 2019-11-20 |
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